Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/067—Polyurethanes; Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/34—Per-compounds with one peroxy-radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver

Definitions

• the present invention relates to a curable resin composition, an adhesive or sealant containing the same, a cured product thereof, and a semiconductor device and electronic component containing the cured product.
• Patent Document 1 discloses a pre-applied underfill material containing a radical polymerizable compound of a specific structure, a radical polymerization initiator, an inorganic filler, and a flexible agent of a specific structure.
• Patent Document 2 discloses a conductive resin composition and a die attachment agent containing the same, characterized in that the conductive resin composition contains (A) a polyethylene glycol di(meth)acrylate of a specific structure, (B) a radical generator, (C) a conductive filler, and (D) at least one selected from the group consisting of linear alkanediol di(meth)acrylate having a linear alkylene group having 5 to 14 carbon atoms, monofunctional and bifunctional polyester (meth)acrylates, and terminal-modified polybutadiene rubber.
• A a polyethylene glycol di(meth)acrylate of a specific structure
• B a radical generator
• C a conductive filler
• D at least one selected from the group consisting of linear alkanediol di(meth)acrylate having a linear alkylene group having 5 to 14 carbon atoms, monofunctional and bifunctional polyester (meth)acrylates, and terminal-modified polybutadiene rubber.
• Curable resin compositions for adhesives used in IoT applications such as smartphones, for example for camera modules, are required to be able to cure at low temperatures of 80°C or less.
• resin compositions for adhesives are required to have a long pot life and good storage stability.
• the pre-applied underfill material disclosed in Patent Document 1 requires high-temperature processing at 150 to 350°C for thermal curing.
• the conductive resin composition disclosed in Patent Document 2 also requires processing at a temperature of about 150°C for thermal curing.
• thermally radically polymerizable resin compositions contain large amounts of highly reactive radical initiators to enable curing at low temperatures. In this case, the curing reaction may proceed at an unintended temperature, shortening the pot life.
• the present invention aims to provide a curable resin composition and adhesive that can be cured at low temperatures, for example, 50 to 100°C, preferably 80°C, and that has a long pot life.
• a first embodiment of the present invention is the following resin composition.
• (1) (A) a radically polymerizable curable compound; (B) inorganic particles; (C) an organic peroxide having a dicarbonate structure represented by the following formula (1),
• a curable resin composition comprising: In the formula (1), R 1 and R 2 are each independently an alkyl group having at least 11 carbon atoms.
• (2) The curable resin composition according to (1) above, wherein the weight average molecular weight of the (C) organic peroxide is 400 or more.
• (3) The curable resin composition according to (1) or (2) above, wherein the organic peroxide (C) has a 10-hour half-life temperature of 70° C. or lower.
• the second embodiment of the present invention is (10) an adhesive or sealant containing the curable resin composition described in any one of (1) to (9) above.
• a third embodiment of the present invention is the following cured product.
• (11) A cured product obtained by curing the curable resin composition according to any one of (1) to (9) above, or the adhesive or sealant according to (9) above.
• the fourth embodiment of the present invention is (13) a semiconductor device or electronic component that includes the cured product described in (11) or (12) above.
• the first embodiment of the present invention it is possible to provide a curable resin composition that can be cured at a low temperature, for example, 50 to 100°C, preferably 80°C, and has a long pot life.
• the second embodiment of the present invention it is possible to provide an adhesive or sealant that can be cured at a low temperature, for example, 50 to 100°C, preferably 80°C, and has a long pot life.
• the third embodiment of the present invention it is possible to provide a cured product that has an appropriate room temperature elastic modulus depending on the application and is useful as a conductive material or insulating material.
• the fourth embodiment of the present invention it is possible to provide a semiconductor device or electronic component that includes a cured product that has an appropriate room temperature elastic modulus depending on the application and is useful as a conductive material or insulating material.
• the general term “pot life” refers to the time during which a resin composition maintains a usable state after preparation.
• the viscosity of the resin composition immediately after preparation is taken as 1.0, and the rate of change in viscosity of the resin composition left for a certain period of time is calculated as the viscosity increase ratio, and the time at which the viscosity increase ratio becomes 1.5 times or more is taken as the pot life (unit: hour) of the resin composition.
• the term "(meth)acryloyl group” includes both methacryloyl groups and acryloyl groups
• the term “(meth)acrylate compound” includes both acrylate compounds and methacrylate compounds.
• the weight average molecular weight refers to a value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.
• the average particle size (D50) of inorganic particles including conductive particles and insulating particles refers to the particle size (median size) at a cumulative frequency of 50% in a volume-based particle size distribution measured by a laser diffraction/scattering method.
• the curable resin composition according to the first embodiment of the present invention comprises: (A) a radically polymerizable curable compound; (B) inorganic particles; (C) an organic peroxide having a dicarbonate structure represented by the following formula (1), Including, In the formula (1), R 1 and R 2 are each independently an alkyl group having at least 11 carbon atoms. According to the present embodiment, it is possible to provide a curable resin composition that can be cured at a low temperature of, for example, 50 to 100° C., preferably 80° C., and has a long pot life.
• the resin composition of this embodiment contains (A) a radical polymerizable curable compound (hereinafter also referred to as "component (A)").
• (A) Radical polymerizable curable compound imparts curability and adhesiveness to the resin composition.
• (A) Radical polymerizable curable compound has a relatively fast polymerization rate, so that curing can be performed quickly.
• (A) Radical polymerizable curable compound is not particularly limited as long as it has radical polymerizability, and examples thereof include, but are not limited to, (meth)acrylate compounds, bismaleimide compounds, and the like.
• the radically polymerizable curable compound preferably includes at least one selected from the group consisting of (meth)acrylate compounds and bismaleimide compounds, and may include two.
• the radically polymerizable curable compound preferably includes a (meth)acrylate compound.
• the (meth)acrylate compound includes a urethane (meth)acrylate compound
• the radically polymerizable curable compound preferably includes a urethane (meth)acrylate compound.
• the radically polymerizable curable compound preferably includes a bismaleimide compound.
• the radically polymerizable curable compound (A) may contain, for example, a single (meth)acrylate compound other than a urethane (meth)acrylate compound, or may contain two types of compounds, a (meth)acrylate compound other than a urethane (meth)acrylate compound and a urethane (meth)acrylate compound, or may contain two types of compounds, a (meth)acrylate compound other than a urethane (meth)acrylate compound and a bismaleimide compound, or may contain three types of compounds, a (meth)acrylate compound other than a urethane (meth)acrylate compound, a bismaleimide compound, and a urethane (meth)acrylate compound.
• the radically polymerizable curable compound (A) is preferably liquid at 25°C. This eliminates the need for a solvent in the resin composition, making it possible to prevent the occurrence of voids when the resin composition is used.
• the content of the solvent in the resin composition of this embodiment is preferably less than 3 mass% relative to the total mass of the resin composition, more preferably less than 1 mass%, and even more preferably 0 mass% (solvent-free).
• the content of the radically polymerizable curable compound (A) in the resin composition is preferably 4 to 90 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 7 to 30 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.
• the content of the radically polymerizable curable compound (A) in the resin composition is preferably 75 to 99 parts by mass, more preferably 80 to 98 parts by mass, even more preferably 85 to 97 parts by mass, and especially preferably 90 to 97 parts by mass, relative to 100 parts by mass of the total amount of all organic substances contained in the resin composition.
• the (meth)acrylate compound may be any compound having at least one (meth)acryloyl group in the molecule, and examples of such compounds include monofunctional (meth)acrylate compounds having one (meth)acryloyl group and polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups.
• Examples of monofunctional (meth)acrylate compounds include, but are not limited to, alkyl (meth)acrylates in which the alkyl group has a branched structure, such as isobutyl (meth)acrylate and t-butyl (meth)acrylate; esters of (meth)acrylic acid and alicyclic alcohols, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; esters of (meth)acrylic acid and cyclic alcohols, such as cyclic trimethylolpropane formal (meth)acrylate; esters of (meth)acrylic acid and aromatic alcohols, such as phenoxyethyl (meth)acrylate; acid-modified mono(meth)acrylates, such as phosphoric acid-modified (meth)acrylates; and (meth)acrylamide compounds, such as hydroxyethyl (meth)acrylamide.
• polyfunctional (meth)acrylate compound examples include alkyl (meth)acrylates such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as tripropylene glycol di(meth)acrylate; polyester (meth)acrylates, and bifunctional (meth)acrylates such as neopentyl glycol modified trimethylolpropane di(meth)acrylate; trimethylolpropane tri(meth)acrylate, and the like.
• alkyl (meth)acrylates such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)
• polyfunctional (meth)acrylate examples include, but are not limited to, trifunctional (meth)acrylates such as acrylates; tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate; (meth)acrylates containing a cyclic structure such as dimethylol-tricyclodecane di(meth)acrylate; acid-modified poly(meth)acrylates such as phosphoric acid-modified poly(meth)acrylate; urethane (meth)acrylates having a urethane bond and a (meth)acryloyl group.
• trifunctional (meth)acrylates such as acrylates
• tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth
• the polyfunctional (meth)acrylate compound when flexibility is required for the cured product of the resin composition, is preferably one having a linear alkylene skeleton having 4 or more carbon atoms or a linear oxyalkylene skeleton having 4 or more carbon atoms between adjacent (meth)acryloyl groups. In one embodiment, when flexibility is required for the cured product of the resin composition, the polyfunctional (meth)acrylate compound is preferably a bifunctional (meth)acrylate compound.
• the (meth)acrylate compound contains a monofunctional (meth)acrylate compound. In one embodiment, from the viewpoint of improving reactivity, it is preferable that the (meth)acrylate compound contains a polyfunctional (meth)acrylate compound. In one embodiment, it is preferable that the (meth)acrylate compound contains a monofunctional (meth)acrylate compound and a polyfunctional (meth)acrylate compound. In one embodiment, it is preferable that the (meth)acrylate compound contains a monofunctional (meth)acrylate compound and a bifunctional (meth)acrylate compound.
• the (meth)acrylate compound when flexibility is required for the cured product of the resin composition, preferably includes a (meth)acrylate compound having a glass transition temperature (Tg) of 15°C or less. In one embodiment, from the viewpoint of suppressing curing inhibition due to oxygen on the surface of the cured product and tack (stickiness) resulting therefrom, the (meth)acrylate compound preferably includes a (meth)acrylate compound having a glass transition temperature (Tg) of more than 15°C.
• the (meth)acrylate compound preferably includes a (meth)acrylate compound having a glass transition temperature (Tg) of 15°C or less and a (meth)acrylate compound having a glass transition temperature (Tg) of more than 15°C.
• the glass transition temperature (Tg) of the (meth)acrylate compound can be measured by a dynamic mechanical analyzer (DMA) as the glass transition temperature (Tg) when made into a homopolymer.
• DMA dynamic mechanical analyzer
• Tg glass transition temperature
• DMA dynamic mechanical analyzer
• the (meth)acrylate compounds may be used alone or in combination of two or more.
• component (A) contains a (meth)acrylate compound
• the content of the (meth)acrylate compound is preferably 3 to 100 parts by mass, more preferably 5 to 80 parts by mass, and even more preferably 8 to 75 parts by mass, per 100 parts by mass of component (A).
• the (meth)acrylate compound includes a urethane (meth)acrylate compound.
• component (A) can include a urethane (meth)acrylate compound.
• a urethane (meth)acrylate compound is an oligomer having a urethane bond and a (meth)acryloyl group, and is obtained by reacting the hydroxyl group and the isocyanate group of the three main raw materials, hydroxy (meth)acrylate, diisocyanate, and polyol.
• various properties can be imparted to the obtained urethane (meth)acrylate compound.
• main raw material polyol when the main raw material polyol is an ether-based compound, it has excellent hydrolysis resistance and flexibility.
• main raw material polyol when the main raw material polyol is an ester-based compound, it has excellent heat resistance, flexibility, and toughness.
• main raw material polyol when the main raw material polyol is a carbonate-based compound, it has excellent heat resistance, weather resistance, and toughness.
• the weight average molecular weight of the urethane (meth)acrylate compound is preferably 1,600 to 20,000, more preferably 2,000 to 18,000, and even more preferably 3,000 to 15,000. However, from the viewpoint of workability and reactivity of the resin composition, it is preferable that the urethane (meth)acrylate compound does not substantially contain a urethane (meth)acrylate compound having a weight average molecular weight exceeding 20,000. It is also preferable that the urethane (meth)acrylate compound does not substantially contain a urethane (meth)acrylate compound having a weight average molecular weight less than 1,600.
• substantially free means that the component is not intentionally included, specifically, that the component is present in the curable resin composition in an amount of less than 0.1% by mass.
• the urethane (meth)acrylate compounds may be used alone or in combination of two or more.
• component (A) contains a urethane (meth)acrylate compound
• the content of the urethane (meth)acrylate compound is preferably 5 to 75 parts by mass, more preferably 6 to 50 parts by mass, and even more preferably 7 to 30 parts by mass, per 100 parts by mass of component (A).
• component (A) contains a bismaleimide compound.
• bismaleimide compound there are no particular limitations on the bismaleimide compound, and any compound having a chemical structure sandwiched between two maleimide groups may be used.
• bismaleimide compounds include N,N'-(4,4'-diphenylmethane) bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylene bis Maleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimidehexane, 1,2-bismaleimideethane (N,N'-ethylene dimaleimide), N,N'-(1,2-phenylene) bismaleimide, N,N'-1,4-phenylene dimaleimide, N,N'-(sulfonyldi-p-phenylene) di
• the bismaleimide compound is preferably a bismaleimide compound having a hydrocarbon group derived from a dimer acid.
• a bismaleimide compound having a hydrocarbon group derived from a dimer acid are described, for example, in JP 2015-193725 A. Hydrocarbon groups derived from dimer acids do not have crosslinkable reactive groups in the molecular chain, and are therefore thought to be able to reduce the room temperature modulus.
• Commercially available bismaleimide compounds having a hydrocarbon group derived from a dimer acid include, but are not limited to, products named "BMI-1500" and "BMI-1700" which are liquid at 25°C, and "BMI-3000” which is solid at 25°C (all manufactured by Designer Molecules Inc.).
• the bismaleimide compound may be either liquid at 25°C or solid at 25°C, but is preferably liquid at 25°C.
• the weight average molecular weight of the bismaleimide compound is preferably 500 to 7000, more preferably 700 to 5500, and even more preferably 800 to 3000.
• the bismaleimide compounds may be used alone or in combination of two or more.
• component (A) contains a bismaleimide compound
• the content of the bismaleimide compound is preferably 5 to 40 parts by mass, and more preferably 15 to 35 parts by mass, per 100 parts by mass of component (A).
• the resin composition of the present embodiment contains (B) inorganic particles (hereinafter also referred to as “component (B)”).
• component (B) examples include (B1) conductive particles and (B2) insulating particles.
• the (B1) conductive particles are used to impart thermal conductivity and/or electrical conductivity to a resin composition and its cured product.
• the resin composition containing the (B1) conductive particles can also be used as a conductive adhesive for bonding electronic components.
• the term "conductive particles” refers to particles having an average particle size of 0.01 ⁇ m to 100 ⁇ m and an electrical conductivity of 10 6 S/m or more.
• the (B1) conductive particles may be particles formed from a conductive material, or may be particles in which a core (core particle) is coated with a conductive material (coated powder).
• the core contained in the conductive particles may be made of a non-conductive material as long as a part of the core is coated with a conductive material.
• the (B1) conductive particles include metal powder and coated powder.
• the conductive material in the (B1) conductive particles is not particularly limited as long as it imparts thermal conductivity and/or electrical conductivity to the resin composition, and examples thereof include, but are not limited to, gold, silver, nickel, copper, palladium, platinum, bismuth, tin, and alloys thereof (particularly, bismuth-tin alloys, solder, etc.), aluminum, indium tin oxide, silver-coated copper, silver-coated aluminum, metal-coated glass spheres, silver-coated fibers, silver-coated resins, antimony-doped tin, tin oxide, carbon fibers, graphite, carbon black, and mixtures thereof.
• the conductive material in the (B1) conductive particles is preferably at least one metal selected from the group consisting of silver, nickel, copper, tin, aluminum, silver alloys, nickel alloys, copper alloys, and aluminum alloys, more preferably at least one metal selected from the group consisting of silver, copper, and nickel, even more preferably silver or copper, and particularly preferably containing silver.
• the (B1) conductive particles are preferably silver particles.
• the (B1) conductive particles are preferably copper particles.
• the silver particles or copper particles include silver powder or copper powder, and a coating powder in which at least a portion of the surface of the core (core particle) is coated with silver or copper.
• the shape of the conductive particles is not particularly limited, and may be any of spherical, amorphous, flake-like (scale-like), filament-like (needle-like), dendritic, etc.
• Flake-like refers to a shape with an aspect ratio of 2 or more, expressed as "long diameter/short diameter", and includes flat shapes such as plate-like and scale-like.
• the long diameter and short diameter of the conductive particles refer to the average values of the long diameter and short diameter of any 20 particles based on an image obtained from a scanning electron microscope (SEM).
• the "long diameter” refers to the longest diameter of a line segment passing through the approximate center of gravity of the particle in a particle image obtained by SEM
• the “short diameter” refers to the shortest diameter of a line segment passing through the approximate center of gravity of the particle in a particle image obtained by SEM.
• the conductive particles may include particles of different shapes.
• the silver particles preferably have a tap density of 1.5 g/cm 3 or more, and more preferably 2.0 to 6.0 g/cm 3.
• the tap density is a value measured in accordance with JIS Z2512 Metal Powder - Tap Density Measurement Method.
• the conductive particles are silver particles
• their average particle size (D50) is preferably 0.05 ⁇ m to 50 ⁇ m, more preferably 0.1 ⁇ m to 20 ⁇ m, and even more preferably 0.1 ⁇ m to 15 ⁇ m, from the viewpoints of the fluidity of the resin composition and the conductivity of the cured product.
• the BET specific surface area thereof is preferably 4.0 m 2 /g or less, and more preferably 0.1 to 3.0 m 2 /g, from the viewpoints of the viscosity of the resin composition and the electrical conductivity of the cured product.
• the conductive particles may be of any one type or of two or more types.
• the content of the (B1) conductive particles in the resin composition is, for example, 95 parts by mass or less, for example, 92 parts by mass or less, relative to 100 parts by mass of the total amount of the resin composition.
• the content of the (B1) conductive particles in the resin composition is preferably 10 to 95 parts by mass, more preferably 20 to 95 parts by mass, even more preferably 50 to 95 parts by mass, and may be 70 to 95 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.
• the (B2) insulating particles can reduce the linear expansion coefficient of the cured product obtained by curing the resin composition, improving thermal cycle resistance.
• the resin composition containing the (B2) insulating particles can also be used as an insulating adhesive or sealant for bonding and protecting electronic components.
• the (B2) insulating particles are not particularly limited as long as they are made of granular bodies formed from an insulating inorganic material and have the effect of lowering the linear expansion coefficient when added.
• insulating inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride.
• silica particles it is preferable to use silica particles because it is possible to increase the loading amount.
• amorphous silica is preferable.
• the (B2) insulating particles may be surface-treated with a coupling agent such as a silane coupling agent.
• the shape of the insulating particles is not particularly limited, and may be any shape, such as spherical, irregular, flake-like (scale-like), filament-like (needle-like), or dendritic.
• the insulating particles are silica particles, their average particle size (D50) is preferably 0.01 to 20 ⁇ m, more preferably 0.05 to 15 ⁇ m, and even more preferably 0.1 to 10 ⁇ m.
• the insulating particles may be of any one type or of two or more types.
• the content of the insulating particles (B2) is preferably 0.1 to 80 parts by mass, more preferably 1 to 75 parts by mass, and even more preferably 10 to 70 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.
• the resin composition of the present embodiment contains (C) an organic peroxide having a dicarbonate structure represented by formula (1) (hereinafter also referred to as “component (C)”).
• component (C) are each independently an alkyl group having at least 11 carbon atoms.
• the alkyl group may be linear, branched, or cyclic, or any combination thereof.
• R 1 and R 2 may be the same or different.
• the number of carbon atoms in the alkyl group represented by R 1 and R 2 is preferably 11 to 30, more preferably 11 to 20, and even more preferably 12 to 20.
• the alkyl group is preferably linear.
• component (C) is preferably a solid at 25° C.
• the average particle size of component (C) is preferably 1 ⁇ m to 400 ⁇ m.
• the average particle size refers to the value of the volume cumulative 50% particle size (D50), and is a value obtained from the volume-based particle size distribution measured using a laser diffraction particle size distribution measuring device and a measuring device using a dynamic light scattering method.
• organic peroxides generate active radicals by cleavage at a certain temperature.
• the active radicals initiate the radical polymerization reaction of the radically polymerizable curable compound.
• the curing reaction may proceed at an unintended temperature, shortening the pot life.
• component (C) has a dicarbonate structure, radicals are efficiently generated at low temperatures, for example, 50 to 100°C, preferably 80°C, and a termination reaction in which the radicals are deactivated is unlikely to occur, so that the initiation reaction and growth reaction of the radical polymerization reaction of the resin composition proceed efficiently.
• component (C) since component (C) has side chains R 1 and R 2 with relatively large molecular weights, the activation energy of component (C) is large and it is more stable at room temperature (for example, about 25°C) during storage.
• component (C) it is possible to provide a curable resin composition that can be cured at a low temperature of 50 to 100°C and has a long pot life.
• the weight average molecular weight of component (C) is preferably 400 or more, more preferably 450 or more, and even more preferably 500 or more.
• the upper limit of the weight average molecular weight of component (C) is not particularly limited, but is, for example, 1500 or less, 1200 or less, or 1000 or less.
• the 10-hour half-life temperature (T10) of component (C) is preferably 70°C or less, more preferably 35 to 70°C, and even more preferably 40 to 70°C.
• the 10-hour half-life temperature (T10) of component (C) of 70°C or less is an index showing the radical generating ability of component (C) at low temperatures of 50 to 100°C, and its stability at room temperature.
• Component (C) may be used alone or in combination of two or more types.
• the content of component (C) in the resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of the radically polymerizable curable compound (A).
• the resin composition of this embodiment may contain optional components other than the above components (A) to (C), such as those described below, as necessary, if desired.
• the resin composition of the present embodiment may contain (D) a polymerization inhibitor (hereinafter also referred to as "component (D)").
• the (D) polymerization inhibitor is a compound having a radical scavenging ability.
• the (D) polymerization inhibitor a known polymerization inhibitor can be used, examples of which include, but are not limited to, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, hydroquinone, p-benzoquinone, etc. Also, known polymerization inhibitors disclosed in JP-A-2010-117545 and JP-A-2008-184514, etc., can be used. As the (D) polymerization inhibitor, any one type may be used, or two or more types may be used in combination.
• the content of (D) the polymerization inhibitor is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 4.0 parts by mass, and even more preferably 0.3 to 3.0 parts by mass, per 100 parts by mass of component (C).
• the resin composition of the present embodiment may further contain, if desired, other additives, such as carbon black, titanium black, coupling agents, ion trapping agents, leveling agents, antioxidants, defoamers, viscosity modifiers, flame retardants, colorants, plasticizers, etc., within the scope of the present embodiment.
• additives such as carbon black, titanium black, coupling agents, ion trapping agents, leveling agents, antioxidants, defoamers, viscosity modifiers, flame retardants, colorants, plasticizers, etc.
• the type and amount of each additive are the same as in the conventional manner.
• the method for producing the resin composition of this embodiment is not particularly limited.
• components (A) to (C), and, if necessary, components (D) and (E) and other additives can be introduced simultaneously or separately into an appropriate mixer, and mixed by stirring to form a homogeneous composition, thereby obtaining the resin composition of this embodiment.
• This mixer is not particularly limited, but a Raikai mixer, Henschel mixer, triple roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirring device and a heating device can be used. These devices may also be used in appropriate combination.
• the resin composition thus obtained is thermosetting and can be cured at low temperatures, for example, 40 to 120°C, preferably 50 to 100°C, more preferably 70 to 90°C, and even more preferably 80°C. At a temperature of 80°C, it is preferable for the composition to cure within 4 hours, more preferably within 3 hours, and even more preferably within 1 hour.
• the curable composition of this embodiment is used to manufacture a semiconductor module containing components that deteriorate under high temperature conditions, it is preferable to thermally cure the composition at a temperature of 50 to 100°C for 15 minutes to 4 hours, preferably 30 minutes to 2 hours.
• the resin composition of this embodiment can be used, for example, as an adhesive or sealant for fixing, joining, or protecting components that constitute a semiconductor device or electronic component, or as a raw material thereof.
• the method of applying the resin composition of this embodiment is not particularly limited, and for example, it can be supplied to a desired portion of a substrate or the like by a known printing method, dispensing method, or coating method.
• Printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, flexographic printing, and the like.
• Dispensing methods include, but are not limited to, methods using a jet dispenser, an air dispenser, and the like.
• Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, and the like.
• the adhesive or sealant according to the second embodiment of the present invention includes the resin composition according to the first embodiment.
• This adhesive or sealant enables good fixing, bonding or protection of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond or protect components constituting a semiconductor device or electronic component.
• engineering plastics e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.)
• semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits.
• the adhesive or sealant of the present embodiment can be cured under low temperature conditions, and therefore has high productivity and is suitable for use, for example, in the manufacture of semiconductor devices and electronic components.
• the cured product of the third embodiment of the present invention is a cured product obtained by curing the resin composition of the first embodiment or the adhesive or sealant of the second embodiment.
• a conductive cured product or an insulating cured product can be provided.
• the "room temperature modulus” refers to the degree of rigidity and flexibility at room temperature exhibited by a cured product of a certain resin composition. The higher the room temperature modulus, the higher the rigidity, and the lower the room temperature modulus, the higher the flexibility. In this embodiment, when moderate flexibility is required for the cured product, the room temperature modulus of the cured product cured at 80°C for 60 minutes is preferably 0.01 to 8.0 GPa, more preferably 0.1 to 7.0 GPa, and even more preferably 0.2 to 6.0 GPa. The room temperature modulus of the cured product can be adjusted by adjusting the type and amount of the components of the resin composition.
• the modulus of elasticity tends to increase as the main chain of component (A) contains a rigid structure such as biphenyl, naphthalene, or dicyclopentadiene, or the amount of a polyfunctional compound as component (A) is increased.
• the elastic modulus tends to be small when the main chain of component (A) contains a hydrocarbon group derived from a long-chain alkyl, long-chain oxyalkylene, polyether, or dimer acid.
• the room temperature elastic modulus can be measured in accordance with JIS C6481 using a dynamic mechanical analyzer (DMA) (e.g., DMA7100, manufactured by Hitachi High-Tech Science Corporation) on a sample coating of a given thickness obtained by curing the resin composition, as shown in the measurement method in the examples described below.
• DMA dynamic mechanical analyzer
• the semiconductor device or electronic component of the fourth embodiment of the present invention includes the cured product of the third embodiment described above, and therefore has high reliability.
• the semiconductor device refers to any device that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc.
• Examples of the semiconductor device or electronic component include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits.
• A Radically polymerizable curable compound (component (A))
• A-1 Cyclic trimethylolpropane formal acrylate (product name: Viscoat #200, manufactured by Osaka Organic Chemical Industry Ltd., monofunctional)
• A-2) Tripropylene glycol diacrylate (product name: TPGDA, manufactured by Daicel Allnex Corporation, bifunctional)
• A-3) Phosphoric acid-modified acrylate (product name: EBECRYL168, manufactured by Daicel Allnex Corporation, 1.5 functional group)
• A-4) Urethane acrylate oligomer 1 (product name: UN-6200, manufactured by Negami Chemical Industries, Ltd., bifunctional)
• A-5) Urethane acrylate oligomer 2 (product name: MBA-2CZ, manufactured by Negami Chemical Industries, Ltd., bifunctional)
• A-6) Urethane acrylate oligomer 3 (product name: UV-3000B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.,
• B Inorganic particles (component (B)) - (B1) Conductive Particles (B1-1): Silver Powder 1 (Product name: EA79613, manufactured by Metalor Technologies Japan Co., Ltd., average particle size (D50): 7 ⁇ m, BET specific surface area: 0.3 m 2 /g, tap density: 5.1 g/cm 3 ) (B1-2): Silver powder 2 (product name: K 79121P, manufactured by Metalor Technologies Japan, average particle size (D50): 7 ⁇ m, BET specific surface area: 2.3 m 2 /g, tap density: 2.7 g/cm 3 ) - (B2) Insulating particles (B2-1): Silica particles (product name: SE5200SEE, manufactured by Admatechs Co., Ltd., average particle size (D50): 2 ⁇ m)
• C An organic peroxide having a dicarbonate structure represented by formula (1) (component (C))
• component (C-1) Dicetyl peroxydicarbonate (product name: Perkadox 24L, manufactured by Kayaku Nouryon Co., Ltd., number of carbon atoms in R 1 and R 2 : each 16, weight average molecular weight: 570.88, 10-hour half-life temperature (T10): 48° C.)
• C-2) Dimyristyl peroxydicarbonate (product name: Perkadox 26, manufactured by Kayaku Nouryon Co., Ltd., number of carbon atoms in R 1 and R 2 : each 14, weight average molecular weight: 514.78, 10-hour half-life temperature (T10): 41° C.)
• C-3) Ditridecyl peroxydicarbonate (manufactured by Alfa Chemistry, R 1 and R 2 each have 13 carbon atoms, weight average molecular weight: 486.72)
• C-4) Distearyl peroxydicarbonate (
• C' Organic peroxide other than component (C) (component (C')) (C'-1): 1,1,3,3-tetrabutyl peroxydecanoate (product name: Luperox 810, manufactured by Arkema Yoshitomi Co., Ltd., weight average molecular weight: 300.5, 10-hour half-life temperature (T10): 44°C) (C'-2): bis(1-methyl-1-phenylethyl) peroxide (product name: Percumyl D, manufactured by NOF Corporation, weight average molecular weight: 270.38, 10-hour half-life temperature (T10): 116.4°C) (C'-3): bis(4-tert-butylcyclohexyl) peroxydicarbonate (product name: Peroyl TCP, manufactured by NOF Corporation, carbon numbers of R1 and R2 : 10 each, weight average molecular weight: 398.55, 10-hour half-life temperature (T10): 40.8°C) (C'-4): di(secondary
• D Polymerization inhibitor (component (D))
• D-1) N-nitroso-N-phenylhydroxylamine aluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• D-2) p-benzoquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• Example 14 and 15 The resin compositions of Examples 14 and 15 were produced in the same manner as in Example 1, except that the component (C-1) used in Example 1 was replaced with the components (C-3) and (C-4), respectively. The properties of the resin compositions of Examples 14 and 15 and the cured products obtained by curing the resin compositions were measured in the same manner as in Example 1.
• the properties of the resin composition and the cured product obtained by curing the resin composition were measured as follows.
• the viscosity of each resin composition in the Examples and Comparative Examples was measured immediately after preparation and after leaving the resin composition at room temperature (about 25°C) for a predetermined time using a Brookfield RVT viscometer (spindle: SC4-14 spindle, measurement temperature: 25°C) at a rotation speed of 10 rpm.
• the viscosity of the resin composition immediately after preparation was taken as 1.0, and the rate of change in viscosity of the resin composition left for a predetermined time was calculated as the viscosity increase ratio, and the time at which the viscosity increase ratio became 1.5 times or more was taken as the pot life (unit: hours) of the resin composition.
• the results are shown in Table 1.
• the pot life of the resin composition is preferably 24 hours or more, more preferably 48 hours or more, and even more preferably 72 hours or more.
• the obtained test piece was measured under the following conditions using a dynamic viscoelasticity measuring device (DMA) (DMA7100, manufactured by Hitachi High-Tech Science Co., Ltd.) in accordance with JIS C6481.
• DMA dynamic viscoelasticity measuring device
• the results are shown in Table 1.
• Deformation mode Tension Measurement mode: Ramp Frequency: 10Hz Strain amplitude: 5 ⁇ m Minimum tension/pressure: 50 mN Tension/Compression Gain: 1.2
• Initial force amplitude 50 mN Movement wait time: 8 seconds Creep wait time factor: 0 Temperature: 25°C.
• the room temperature elastic modulus of the cured product obtained by curing the resin composition at 80°C for 60 minutes is preferably 0.01 to 8.0 GPa, more preferably 0.1 to 7.0 GPa, and even more preferably 0.2 to 6.0 GPa.
• the thickness of the obtained cured film was measured using a surface roughness shape measuring instrument (model number: Surfcom 1500SD-2) manufactured by Tokyo Seimitsu Co., Ltd., and the resistance value was measured using a digital multimeter (model number: 2001) manufactured by TFF Keithley Instruments Co., Ltd., and the volume resistivity was calculated to be the specific resistance value. Note that the measurement was not possible for Comparative Example 2. No measurement was performed for Examples 12 and 13, which do not contain conductive particles. The resistivity is preferably less than 10 ⁇ 10 ⁇ 4 ⁇ cm. The results are shown in Table 1.
• the present invention is a curable resin composition that can be cured under low temperature conditions, and is extremely useful as an adhesive or sealant suitable for use in manufacturing semiconductor devices and electronic components.

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